JPH0784561B2 - Compositions curable to low surface energy materials - Google Patents

Description

FIELD OF THE INVENTION The present invention relates to hydrosilylation reaction products of compounds containing fluorine and aliphatic unsaturation with compounds containing silicon-bonded hydrogen and to low surface energy materials. In another aspect, the invention relates to a substrate having a low surface energy coating of hydrosilylation reaction products.

BACKGROUND OF THE INVENTION Pressure sensitive adhesive tapes that are wound onto themselves in roll form generally have a low adhesion backing coating that allows the tapes to be unwound without delamination. The force required to separate such tapes into low adhesion backing coatings is typically in the range of 150 g to 900 g per 2.5 cm width. If the tape is an adhesive transfer tape that is not wound on itself or in the form of a roll, the adhesive coating is also usually tacky and the pressure sensitive adhesive adheres very weakly, e.g. width 2.5. It is usually protected by a disposable web having a low adhesion coating of about 5 g to 150 g per cm, preferably 5 g to 50 g. This structure is
It is useful in products such as adhesive coated labels or large adhesive coated sheets or adhesive transfer tape constructions. U.S. Pat.Nos. 3,230,289, 3,565,750 and 3,729,44
Specification No. 4 is an example of such a product. Any such low adhesion coatings adhere strongly to the underlying substrate and are either fully cured or incompatible with the adhesive so they do not stain the adhesive, i.e., to the adhesive. Does not transfer and does not unduly interfere with adhesion. Low adhesion backing coatings are disclosed, for example, in U.S. Patents 3,318,852 and 3,536,749.
Nos. 4,057,596 and 4,216,252.

Some pressure sensitive adhesives, especially those made from polydimethyl siloxane, are very strongly adhesive so that tapes containing this adhesive should be removed from known low adhesion coatings, especially after prolonged storage. Requires undesirably high peeling force. The adhesive of such tapes will carry away and thus be contaminated by significant amounts of low adhesion material. Known low-adhesion coatings, such as polyurethane, polytetrafluoroethylene and polydimethylsiloxane, are not particularly effective at providing release forces in the range of 5 to 50 g / 2.5 cm width with polydimethylsiloxane adhesive.

Low adhesion coatings have other applications, such as cookware, aircraft ice release non-stick coatings and lubricious coatings for magnetic recording media.
Such low adhesion coatings are also sometimes referred to by the term "release coating" which may also include mold release agents that are generally effective only by cohesive failure. Lubricants that are uncured fluids or waxes usually work by cohesive failure. The release coating of the present invention is a cured composition intended to resist cohesive failure. In order to distinguish release coatings intended to cohesively fail from those intended to withstand cohesive failure, the latter are referred to herein as "liners", especially "low surface energy liners". Because low surface energy is important for its effectiveness.

Oriorganohydrosiloxanes useful in making the low surface energy coatings of the present invention are known in the art,
Moreover, U.S. Pat.Nos. 3,159,662, 3,220,972 and
No. 3,410,886.

The ethylenically unsaturated perfluoropolyether monomer effective to undergo hydrosilylation in the process of the invention is
It is disclosed in U.S. Pat. Nos. 3,810,874 and 4,321,404.

SUMMARY OF THE INVENTION The present invention provides compositions that can be cured into low surface energy materials that are useful in coated form as a release surface for use with the most aggressive types of adhesives known in the art or for other applications requiring low adhesion. To do.

Briefly, a composition of the present invention that is curable to a low surface energy material comprises: (1) at least two hydrogen atoms bonded to a silicon atom, no more than two hydrogen atoms on any one silicon atom. It has atoms and has a number average molecular weight of 106 to about 50,000.
A polyorganohydrosiloxane having (2) _a segment containing a number of repeating units of the formula Ca F _2a O-, where each unit "a" is independently an integer 1 to 4 and at least one segment An ethylenically unsaturated perfluoropolyether monomer having an ethylenically unsaturated group, preferably having a number average molecular weight of at least 500, most preferably 500 to 20,000, and (3) polyorganohydrosiloxane and ethylenically unsaturated perfluoropolyether It is characterized in that it comprises an effective amount of a hydrosilylation catalyst which results in the condensation of ether monomers.

In another aspect, the invention provides for (1) coating a substrate with a composition as defined above, and (2) exposing the coated substrate to a suitable energy such as heat or actinic radiation. Provided is a method for providing a substrate with a low surface energy coating, ie a low surface energy liner, which comprises hydrosilylation of an organohydrosiloxane with an ethylenically unsaturated perfluoropolyether monomer.

In a further aspect, the present invention provides a low surface energy liner made by the above method. The release performance of the liner to the adhesive using the 180 ° peel test (below) is in the range of about 5 g to 900 g per 2.5 cm width.

In the present invention, "hydrosilylation" means a reaction involving the addition of a silicon-hydrogen group across a pair of aliphatically unsaturated carbon atoms, i.e. carbon atoms linked by a double bond. Is the following Can be represented by the general formula:

"Polyorganohydrosiloxane" has at least two silicon atoms bound together by oxygen atoms, and at least two of the bonds to silicon atoms not bound to oxygen are bound to hydrogen, and Each remaining bond is incorporated into a linear or branched or cyclic structure attached to a carbon atom of an organic group, a molecular weight of 106-50,
It means a silicon-containing compound having a range of 000.

"Perfluoropolyether" is a polyether, i.e. having a chain of at least two alkoxy groups, alkyl groups, which are fully fluorinated and which may be branched or straight-chain containing 1 to 4 carbon atoms. Means a compound.

"Actinic radiation" means any effective radiation, as used in this application, includes ultraviolet and visible rays and also electron beams, "chained" is in the backbone and means a pendant or end group. Without and "low surface energy" means materials such as perfluoropolyether which have low molecular attraction to other materials such as known adhesives and other organic polymers.

"Flexible" means bendable at an angle of 90 ° without breaking.

DETAILED DESCRIPTION OF THE INVENTION The polyorganohydrosiloxanes useful in the hydrosilylation reaction of the present invention include at least two hydrogen atoms bonded to a silicon atom and no more than two hydrogen atoms on any one silicon atom. Preferably, the polyorganohydrosilosiloxane has a molecular weight in the range of 106 to 50,000. Preferably, the organic group is a straight chain group,
Moreover, it has 1 to 12 carbon atoms or is branched or cyclic and has 3 to 12 carbon atoms and optionally up to 3 chain oxygen atoms (two of which are bonded together). Have not). The smallest such compound has the formula And a molecular weight of 106.

The polyorganohydrosiloxanes that can be used in the compositions of the present invention include cyclopolyorganohydrosiloxanes having the empirical formula (R ₂ SiO) _b II and the general formula (In the formula, each R independently represents hydrogen or a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 7 carbon atoms or a cycloalkyl group, and an alkoxy group having 1 May be a substituted or unsubstituted organic group selected from an alkoxyalkyl group having 3 to 3 carbon atoms and a phenyl group, the substituent being one or more halogens (ie chlorine, fluorine, bromine), A C ₁ -C ₄ alkyl group, a linear alkyl group having 1 to 18 carbon atoms,
Selected from branched or cyclic (preferably linear) trifluoroalkyl, alkyl-amide and alkyl-sulfonamido groups and fluoroalkylcarbonyl-amide and fluoroalkylcarbonyl-sulfonamido groups, and at least two Is 70% of all R groups
No more is hydrogen, b is an integer having a value of 3-18, c has a value of 0, 1, 2 or 3 and d is an integer having a value of 1 to about 300) There are preferred linear and branched polyorganohydrosiloxanes that have.

As noted above, polyorganohydrosiloxanes and their preparation are known in the art and are described, for example, in Ashley U.S. Pat.No. 3,159,662, Lamoreaux U.S. Pat.No. 3,220,972 and Joy U.S. Pat. It is disclosed.

The polyorganohydrosiloxane compound or polymer having a structural unit represented by the above formula II or III,
Preferred, but not necessarily, fluorinated organopolysiloxanes which do not have olefinic unsaturation in the radical R but contain silane-based hydrogens are preferred.

Among the organic groups represented by -R are alkyl such as methyl, ethyl, propyl, isopropyl, butyl, octyl and dodecyl, cycloalkyl such as cyclopentyl, cyclohexyl and cycloheptyl, phenyl,
Aryl such as naphthyl, tolyl and xylyl, aralkyl such as benzyl, phenylethyl and phenylpropyl, chloromethyl, trifluoromethyl, 3,
Halogenated derivatives of the above groups such as 3,3-trifluoropropyl, chloropropyl, chlorophenyl, dibromophenyl, tetrachlorophenyl and difluorophenyl, such as 3- (N-ethylperfluorooctanesulfonamido) propyl Sulfonamide alkyl compounds, β-cyanoethyl, γ-cyanopropyl and β
There are cyanoalkyl such as cyanopropyl. R is preferably methyl. Formulas II and III are intended to include those materials in which R is a combination of the above organic groups to provide various structural units. Other polyorganohydrosiloxanes useful in the present invention are those of Walter Noll, "Chemistry and Technology of Silicones".
gy of Silicones ”, 262, 270 and 279, Academic Press, NY (1968).

Materials specifically included in Formulas II and III above are 1,3
-Dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, tetrakis (dimethylsiloxy) -silane etc. and linear and branched polymers containing up to 1,000 or more silicon atoms per molecule . Also within the scope of Formula II above are cyclic materials such as methylhydrogen siloxane cyclic compounds having the formula (CH ₃ SiHO) _{z, where the} subscript z is an integer 3-10. included. In particular, tetramethylcyclotetrasiloxane is included. Within the scope of formulas II and III, hydrogendiene siloxane units (HSiO _1.5 ), methylhydrodiene siloxane units (HSiCH ₃ O), dimethylhydrodiene siloxane units [HSi (CH ₃ ) ₂ O _0.5 ] and dihydrodiene siloxane units. There is a unit (H ₂ SiO). Due to availability, the preferred polyorganohydroxane has the structure Is a linear polymethylhydrosiloxane having the formula: where e is an integer having a value of about 5 to 300.

Preferred ethylenically unsaturated perfluoropolyether monomer used in the compositions of the present invention have the formula _{Q g X (C a F 2a} O) in _f C _{a F 2a} Z IV [wherein, Q is formula (In the formula, R ¹ and R ² are independently hydrogen and one alkyl group
An ethylenic radical having 4 carbon atoms and being linear, branched or cyclic alkyl, phenyl, phenylalkyl or alkylphenyl, and R ¹ and R ² are preferably hydrogen) A saturated group, g is an integer having a value of 1 or 2, X is a polyvalent linking group linking one or two Q groups to the perfluoropolyether segment, and X is 2 when g is 1. It is a valence and is trivalent when g is 2, and (C _a F _2a O) _f C _a F _2a is f units (C _a F _2a O) (wherein “a” of each unit is Independently an integer from 1 to 4,
And f is the value of at least 2, preferably perfluoropolyether segment comprising a chain of a number) having an average of about 3 to 500, and Z is -OC _a F _{2a + 1} or -XQ _q, moreover Z preferably have (wherein, a, X, Q and g are as defined above) -XQ _g of a].

In the above definition of an ethylenically unsaturated perfluoropolyether monomer, any known linking group can be used as long as it does not interfere with the hydrosilylation process, i.e. the sulfur-containing compound does not poison the catalyst. .
These linking groups X generally have a molecular weight of less than 500, preferably 2
It has less than 00 and can consist of atoms selected from carbon, hydrogen, oxygen and nitrogen.

Examples of linking groups are: −CH ₂ OCH ₂ − Is.

Other examples of linking groups and the preparation of ethylenically unsaturated peropolyethers containing them are both referenced in this disclosure of perfluoropolyethers in US Pat. No. 3,811.
No. 0,874 and assignee's copending application 340,473.

A more preferred ethylenically unsaturated perfluoropolyether monomer used in the composition of the present invention has a bonding group X of —CH ₂ OCH ₂ —. and Is a compound of formula IV selected from

Illustrative of the more preferred ethylenically unsaturated perfluoropolyether monomer of formula IV is the formula: and Wherein a, R ² and f are as defined above.

Particularly preferred are Formula _{H 2 C = CHCH 2 OCH 2} CF 2 O (CF 2 CF 2 O) m (CF 2 O) n CF 2 CH 2 OCH 2 CH = CH 2; VIII ( wherein, m and n Is a number each indicating the number of perfluoroethyleneoxy and perfluoromethyleneoxy repeating units randomly distributed, m and n independently have the value 1 to 300, and the ratio m / n is 0.2 / 1 to 5/1. Is an ethylenically unsaturated perfluoropolyether monomer.

Examples of perfluoropolyether monomers of formula IV useful in the preparation of the low energy coatings of the present invention are shown in Table 1 below, with a random distribution of perfluoroalkylene oxide units, the average number of which is otherwise predetermined. .

The compounds of formula IV are ethylenically unsaturated compounds, preferably esters, amides or ethers or these compounds have a combination of these groups. These compounds are obtained from perfluoropolyether alkanols, perfluoropolyether-alkylamines, perfluoropolyether-carboxylic acids, halides or esters or perfluoropolyether-carboxamidols by esterification, amidation known to the skilled chemist. Alternatively, it can be produced by an etherification reaction. That is, the ethylenically unsaturated perfluoropolyether monomer of formula IV is conventionally a corresponding alkyl ester, namely Where a and f are as defined above, and is suitably prepared by a variety of reactions known in the art. For example, reaction of the dimethyl ester with the ethylenically unsaturated primary or secondary amines such as allylamine or diallylamine provides ethylenically unsaturated amides as shown in Formulas VI and VII. Methylol-terminated perfluoropolyethers such as HOCH ₂ (C
_a F _2a O) _f (C _a F _2a ) CH ₂ OH is a useful intermediate to other monomers of formula IV, and is a reduction of said ester, such as lithium aluminum hydride or sodium borohydride. It is produced by the reaction of. Reaction of these alcohols with ethylenically unsaturated halides such as allyl bromide in the presence of sodium hydride or potassium hydroxide provides ethylenically unsaturated perfluoropolyethers as shown by formulas V and VIII. Given. Also, perfluoropolyether alcohols are acyl halides, anhydrides or lower alkyl esters of acrylic acid or methacrylic acid or isocyanatoalkyl acrylates or methacrylates, for example 2
Can be reacted with isocyanatoethylmethacrylate or unsaturated isocyanates such as allylisocyanate to give ethylenically unsaturated perfluoropolyethers. Another effective method for preparing compounds of formula IV is
Reaction of 2 moles of organic diisocyanate and a hydroxyalkyl acrylate with a perfluoropolyether diol such as a methylol terminated perfluoropolyether having the above formula.

Further description of the preparation of ethylenically unsaturated perfluoropolyether monomers useful in the hydrosilylation reaction of the present invention can be found in the disclosures of US Pat. Nos. 3,810,874 and 4,321,404.

Generally, the curable composition comprises from 2% to 35% by weight of polyorganohydrosiloxane of formula II or III together with 65% to 98% by weight of ethylenically unsaturated perfluoropolyether of formula IV, the% by weight being , Per weight of the total composition. For each composition, the force required to separate the adhesive from the release coating varies from about 10 g / width less than 2.5 cm to about 20 g-400 g / width 2.5 cm or more by varying the weight ratio of the components. Can vary to higher values of. For example, the use of higher weight percent of the perfluoropolyether component generally results in lower peel force values with pressure sensitive adhesives. The weight percent of the components used to provide an effective cured coating is also determined by the equivalent weight of each component, ie, the molar ratio of SiH to ethylenically unsaturated functional groups. Molar ratios of about 0.5 to 1.3 generally provide effective coatings.

As the hydrosilylation catalyst used in the composition of the present invention,
There are all known metal-containing catalysts that are effective in catalyzing the hydrosilylation reaction between silicon-bonded hydrogen groups and ethylenically unsaturated groups. Examples of these materials include US Patent No.
A finely divided platinum catalyst as described in 2,970,150,
Chloroplatinic acid catalysts described in U.S. Pat.No. 2,823,218, platinum hydrocarbon complexes taught in U.S. Pat.Nos. 3,159,601 and 3,159,662 and platinum alcoholate catalysts described in U.S. Pat.No. 3,220,972 and 1983 3 years
Assignee's co-filed patent application dated 4th March Platinum complexes with UV-substituted groups as disclosed in US Pat. No. 472,158 and as disclosed in US Pat. No. 4,510,094 (cyclopentadienyl). There are (tri-aliphatic) platinum complexes. Additionally, the platinum chloride-olefin complexes described in US Pat. No. 3,416,946 are useful herein.

When using a platinum catalyst, the platinum catalyst generally causes the co-reaction of the ethylenically unsaturated perfluoropolyether monomer and the polyorganohydrosiloxane in an amount related to the amount of ethylenically unsaturated groups of the perfluoropolyether monomer. Present in sufficient quantity. Satisfactory results can be obtained when the platinum catalyst is present in an amount that provides a small amount of 1 part by weight of platinum per million parts by weight of perfluoropolyether monomer. On the other hand, it is also possible to use a sufficient amount of platinum catalyst to provide a large amount of 1 to 10 parts by weight of platinum per 1,000 parts of perolofuropolyether monomer. However, it is generally preferred to use a sufficient amount of platinum catalyst to provide from 1 to 200 parts by weight of platinum per million parts by weight of perfluoropolyether monomer. Also rhodium,
Metals such as iridium and platinum and their compounds are known to catalyze these hydrosilylation reactions, and their use is intended to be within the scope of the present invention. Platinum compounds are the preferred catalysts.

The compositions of the present invention may also contain hydrosilylation inhibitors, dyes, pigments and reinforcing fillers such as carbon black, fumed silica, titanium dioxide and the like. Further, the release properties of the cured composition can be modified, i.e., the value of force required to separate the adhesive from the surface of the cured composition can be determined by any method known in the art, such as the method described above, per 100 parts of composition. It can be increased by adding 0.1 to 10 parts of release modifier to the composition or by using different primers. The exfoliation modification preferably provides at least 10% differential exfoliation. Such modifiers are known and are described, for example, in U.S. Pat.
Tetraalkoxyalkyl silicates such as Si (OC ₂ H ₄ OC ₂ H ₅ ) ₄ as disclosed in US Pat. No. 325, US Pat.
Graft polymer having polyorganosiloxane segment and organic polymer segment described in 4,366,286, vinyl-terminated diorganopolysiloxane in which 3 mol% to 39 mol% of diorgano units are non-terminal diphenylsiloxane units, and US There is a three-dimensional toluene soluble silicate resin known in the silicate industry as the MQ resin described in patents 2,676,182 and 2,857,356.

The low surface energy materials of the present invention include: a) a polyorganohydrosiloxane, an ethylenically unsaturated perfluoropolyether monomer, a hydrosilylation catalyst and optionally other additives in a solvent such as at least one halogen-containing organic solvent. Providing a composition, either with or without a solvent, b) coating the composition on a substrate, c) removing the solvent in use, and then d) a fraction of 1 second to 5 minutes or more. 25 ° C. to 150 ° C. over a suitable time with the hydrosilylation catalyst of the mixture
It can be applied to the substrate by curing the composition by heating or by applying actinic radiation.

Preferred solvents such as 1,1,2-trichlorotrifluoroethane and perfluorooctane can be used.

Suitable substrates on which the composition can be coated and cured include sheets, fibers and other forms of material. Preferred substrates are polyester, polyamide, polyolefin and polycarbonate films, as well as flexible sheet materials used in pressure sensitive adhesives. Other substrates on which the composition can be coated and cured include glass, ceramics, metals and rubber.

Coating techniques useful in the method of the present invention include brush coating, wire or knife coating, spraying, flow coating, and gravure coating, for example 80 lines per cm.

If the cured coating does not readily adhere to the substrate, it may be desirable to first apply a primer or adhesion promoting coating or treatment known in the art to the substrate.

The primer is a paint of a suspension of colloidal particles in the form of a sol, optionally containing a binder resin. Examples of such coatings are hydrated oxides of one or more elements such as hydrated silica, alumina, tungsten oxide, ferric oxide or titanium oxide taught in US Pat. No. 2,366,516. And combinations thereof, U.S. Pat.No. 2,721,855
Polymeric organosilicon compositions taught in US Pat. No. 3,794,556, mixtures of tetraalkoxysilanes taught in US Pat. No. 3,794,556, or hydrolysates thereof and tetraalkyl titanates and US Pat.
A combination of an organosilane and a hydrolyzable titanium compound taught in 3,321,350.

A substrate having a coating of the cured composition of the present invention on one or both sides is then coated with any of the adhesives known in the art including acrylic adhesives, rubber-based adhesives and silicone adhesives. It can also be covered. The adhesive coated substrate can then be wound onto itself if desired. Pressure sensitive, flexible adhesive coated sheet materials are known in the art. For example, US Re-patent No. 24,906 (acrylate), US Pat. Nos. 2,857,356, 2,814,601 and 2,736,721 (siloxane) and US Pat.
No. 3,925,283 (Urethane) discloses an adhesive coating material using a particularly desirable pressure sensitive adhesive.

The release of the coating from the adhesive can be measured by a variety of methods known in the art depending on whether the final product is rolled up, such as a sheet or tape. Various test methods for pressure sensitive adhesive tapes are described in Pressure-Sensitive Tape Counci.
l) (Test Methodology Reported by (PSTC)
For Prescher-Sensitive Tapes (Test
Methods for Pressure-Sensitive Tapes) "(several editions)
Has been reported. The peeling value shown in the example is the peeling speed of 230 cm / mi.
n and a peel angle of 180 ° can be used.

Peel values for cured perfluoropolyether coated substrates prepared in the examples below were determined by the following procedure.

A test pressure sensitive adhesive tape with polydimethylsiloxane pressure sensitive adhesive was pressed against the surface of the perfluoropolyether coating using a 1.5 kg rubber roller to laminate the pressure sensitive adhesive tape and the cured perfluoropolyether coated substrate. Manufacture things. Cut the laminate into 2.5 x 25 cm strips. The "peel value" is the force (peel force) required to pull the test tape with the adhesive adhered to it off the perfluoropolyether coated substrate at an angle of 180 ° and a pull rate of 230 cm / min.

The readhesion value of the pressure sensitive adhesive tape is determined by the following procedure.

The pressure sensitive tape peeled from the perfluoropolyether coated substrate is applied to the surface of a clean glass plate using a 2 kg rubber roller. The readhesion value is measured by pulling the tape from the glass surface at an angle of 180 ° and a peel rate of 230 cm / min.

The objects and advantages of the present invention will be more specifically illustrated by the following examples, but the particular materials and amounts thereof and other conditions and details detailed in these examples unduly impair the invention. It should not be construed as limiting.

Example 1 Allyl ether terminated perfluoropolyether H ₂ C = CHCH ₂ OCH ₂ CF ₂ O (C ₂ F ₄ O) _m (CF ₂ O) _n CF with a number average molecular weight (Mn) of about 2000 and an m / n ratio of 0.5. ₂ CH ₂ OCH ₂ CH ═CH ₂ 2.05 g, platinum complex in divinyltetramethyldisiloxane as described in US Pat. No. 3,775,452 (Example 1).
002g (added as a solution containing 15% by weight platinum) and
A solution containing 15 ml of 1,1,2-trichlorotrifluoroethane was stirred at 25 ° C. for 15 hours in a closed vial.
Trimethylsilyloxy-terminated polymethylhydrosiloxane 0.075 g and 1,1,2-trichlorotrifluoroethane 8
ml solution was added. Silica-titanium dioxide undercoating poly (ethylene terephthalate) film with No.3 RDS rod (RDSp
ecialties Inc.) was used to coat the solution.
The film was then heated at 95 ° C for 5 minutes in a dryer. A test tape having a polydimethylsiloxane pressure sensitive adhesive was laminated to the side of the film containing the cured coating.
The initial peeling force was 10 g / 2.5 cm to 15 g / 2.5 cm. Laminate
After heat aging at 70 ° C (24 hours), the peel force is
30g / 2.5cm to 40g / 2.5cm, the re-adhesion value (glass) showing adhesion of silicone adhesive after contact with release coating is 1120g /
It was 2.5 cm. For comparison, the adhesion of the test tape before contact with the release coating was 1100 g / 2.5 cm to 1120 g / 2.5 cm.

A silica-titanium dioxide subbing poly (ethylene terephthalate) film is a 62.5 micrometer thick poly (ethylene terephthalate) film reversed with a solution of 94 parts by weight absolute ethanol, 3 parts by weight glacial acetic acid and 3 parts by weight tetraisopropyl titanate. It was manufactured by roll coating. Then, the coated film is
It was dried for 1.5 to 2 minutes at 0 ° C. and then overcoated with Ludox ^™ LF (DuPont), a 50% by volume aqueous ethanol solution containing about 0.5% by weight of colloidal silica. The coating was then dried at about 95 ° C for 1.5-2 minutes. Similar results were obtained with substrates primed with an alcoholic solution that was 1% to 10% by weight in both tetraisopropyl titanate and colloidal silica.

Example 2 An unprimed poly (ethylene terephthalate) film was coated using the coating solution and procedure described in Example 1,
It was then heated at 95 ° C for 5 minutes. After heat aging the laminate, the peel force and re-adhesion value are 100g / 2.5cm ~ 11 respectively
It was 0 g / 2.5 cm and 1090 g / 2.5 cm-1120 g / 2.5 cm.

Example 3 Using the procedure described in Example 1, an ethylenically unsaturated perfluoropolyether having a number average molecular weight of 2000 and an m / n ratio of 0.5. 1.15 g, 0.002 g of platinum catalyst solution described in Example 1, DC-1107
0.1 g and 1,1,2-trichlorotrifluoroethane 15 ml
Was coated onto a poly (vinylidene chloride) -priming poly (ethylene terephthalate) film using a No. 3 RDS rod. The film was then heated to 95 ° C for 5 minutes. After thermal aging (70 ° C. for 24 hours) of a laminate prepared from the silicone adhesive test tape described in Example 1, the peel force is 60 g / 2.5 cm to 90 g / 2.5 cm and the readhesion value is 950 g / 2.5 cm.
It was ~ 980g / 2.5cm.

Example 4 Perfluoropolyether diacrylate having a number average molecular weight of about 1900 and an m / n ratio of 0.5. 2.0 g, 0.002 g of the platinum catalyst solution described in Example 1, 0.2 g of polymethylhydrosiloxane fluid DC-1107 and 1,1,2-
A solution containing 20 ml of trichlorotrifluoroethane was coated onto a poly (vinylidene chloride) -priming poly (ethylene terephthalate) film (No. 3 RDS bar). Then
The coated film was heated at 90 ° C for 10 minutes. The peel strength of the laminate produced from the test tape described in Example 1 was 170 g / 2.5
cm-220g / 2.5cm, and the re-adhesion value is 895g / 2.5cm-
It was 960g / 2.5cm.

Example 5 This example shows the stripping performance of the general structure allyl ether terminated perfluoropolyether shown in Example 1, but with a higher average molecular weight of about 3800 and an m / n ratio of 0.5. 1.10 g of allyl ether, 0.0015 g of the platinum catalyst solution described in Example 1, DC-11
07 0.03 g and 1,1,2-trichlorotrifluoroethane
A solution containing 12 ml was coated onto a silica-titanium dioxide primed poly (ethylene terephthalate) film using a No. 3 RDS rod. The coated film was heated to 100 ° C for 3 minutes.
After thermal aging of the laminate of the silicone adhesive test tape described in Example 1 (70 ° C. 3 days), the peel force is 10 g / 2.5-2.
0g / 2.5cm, and the re-adhesion value is 1010g / 2.5cm-1060g
It was /2.5 cm.

Example 6 This example demonstrates the performance of a coating obtained by using a fluorine-containing polymethylhydrosiloxane. Fluorine 46.9% and an average 18 _{C 8 F 17 SO 2 N (} C 2 H 5) (CH 2) 3 Si (CH 3) O
-And containing 17 CH ₃ SiHO-siloxane units and having the general formula 0.25 g of trimethylsilyloxy terminated capped linear fluorosilicone, 0.5 g of allylamide terminated capped perfluoropolyether as described in Example 3 and
A solution containing 15 ml of 1,1,2-trichlorotrifluoroethane was coated onto a poly (vinylidene chloride) primed poly (ethylene terephthalate) film using a No. 3 RDS rod. The film was heated at 90 ° C for 5 minutes. The peel strength of the laminate of the silicone adhesive test tape described in Example 1 is
110g / 2.5cm-170g / 2.5cm, and the re-adhesion value is 1010g /
It was 2.5 cm to 1060 g / 2.5 cm.

Examples 7 to 11 These examples (Table 1) demonstrate that the properties of cured release coatings can be varied by varying the ethylenically unsaturated perfluoropolyether / polyorganohydrosiloxane weight ratio used in the coating formulation. Is shown. Weight ratio 93
I examined / 7-97 / 3. In these experiments, allyl ether terminated perfluoropolyether, polymethylhydrosiloxane fluid and the platinum catalyst described in Example 1 (platinum 200 p
pm) was used. These release coatings (0.5 micrometer thick) were prepared by casting a solution of the above components (6% by weight) in 1,1,2-trichlorotrifluoroethane onto a silica-titanium dioxide basecoat poly (ethylene terephthalate) film. And then curing the coating at 95 ° C. for 5 minutes. Peel force and readhesion values for laminates made from the silicone adhesive test tape described in Example 1 are shown in Table 1.

Example 12 A release liner comprising a cured release coating of allyl ether terminated perfluoropolyether on a silica-titanium dioxide primed poly (ethylene terephthalate) film was prepared according to Example 1
Prepared using the procedure described in. The side of this liner containing the release coating was coated with a knife coater on a silicone adhesive (DC in 1,1,2-trichlorotrifluoroethane).
-355, Dow Corning) with 18% by weight solution (thickness 200 micrometers). The adhesive coated liner was dried at 25 ° C for 20 hours and then laminated to the unprimed poly (ethylene terephthalate) film by pressing the adhesive side between two rubber rollers. The initial peel force required to separate the uncoated polyester film containing the adhesive from the release liner is 5g / 2.5cm ~
It was 15 g / 2.5 cm. After heat aging at 70 ° C. (7 days), the peel strength was 20 g / 2.5 cm to 30 g / 2.5 cm and the readhesion value (glass) was 1400 g / 2.5 cm to 1460 g / 2.5 cm. For comparison, the adhesion of the silicone adhesive before contacting the release coating was determined to be 1680 g / 2.5 cm to 1800 g / 2.5 cm.

Example 13 This example demonstrates the preparation of a silicone adhesive transfer tape containing a perfluoropolyether release coating. The allyl ether terminated perfluoropolyether, polymethylhydrosiloxane fluid (DC-1107) and platinum catalyst described in Example 1 were used in a release coating formulation. The coating solution was 145 g of allyl ether terminated perfluoropolyether, DC-1107.
It contains 5.3 g, 0.2 g of platinum catalyst solution and 1.5 of 1,1,2-trichlorotrifluoroethane. Silica-titanium dioxide basecoat Poly (ethylene terephthalate) film (basecoat on one side only) is coated with the above solution using a 200-line gravure coater on one side of a 15 cm x 200 m roll, then the coated film at 120 ° C It was cured by passing through a dryer for 10 minutes. The article was then coated with the same solution on the other side and then cured under similar conditions to give a release liner having a cured perfluoropolyether release coating about 1 micrometer thick on both sides of the substrate. Obtained. 1,
18 of silicone pressure sensitive adhesive (DC-355, Dow Corning) in 1,2-trichloro-2,2,1-trifluoroethane
The wt% solution was knife coated onto the release coating on the unprimed surface. The adhesive coated liner can be air dried and then the liner can be wound onto itself to form a jumper that can be slit into a smaller roll of tape if desired. When the tape is unwound, the adhesive adheres to the release coating coated on the unprimed surface of the polyester substrate. After contacting a portion of the adhesive surface of the rewind tape with a clean glass surface using a rubber roller, the release of the liner containing the perfluoropolyether release coating is facilitated to ensure complete adhesion of the silicone adhesive to the glass surface. A transfer is obtained.

Various modifications and alterations to this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention, and that this invention is not unduly limited to the exemplary embodiments set forth herein. Should not understand.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/54 C08L 71/02 LQE C09D 183/05 PMS C09J 7/02 JKV

Claims (3)

[Claims] [Claim 1] 1. The following formula (R ₂ SiO) _b II and (In the formula, each R is independently hydrogen or a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 7 carbon atoms in the ring, a cycloalkyl group or an alkoxy group. A substituted or unsubstituted organic group selected from an alkoxyalkyl group having 1 to 3 carbon atoms and a phenyl group, the substituent being one or more halogens, a C _{1 to} C ₄ alkyl group, Linear, branched or cyclic trifluoroalkyl, alkyl-amide and alkyl-sulfonamido groups and fluoroalkylcarbonyl-amide and fluoroalkylcarbonyl-sulfonamido groups in which the alkyl group has 1 to 18 carbon atoms 70 of all R groups selected from
% Is hydrogen, b is an integer having a value of 3-18, c has a value of 0, 1, 2 or 3 and d is an integer having a value of 1-300) A polyorganohydrosiloxane having a selected formula, 2. The following formula Q _g X (C _a F _2a O) _b C _a F _2a Z IV [wherein Q is a formula (In the formula, R ¹ and R ² are independently hydrogen and one alkyl group
An ethylenically unsaturated group having 4 carbon atoms and having linear, branched or cyclic alkyl, phenyl, phenylalkyl or alkylphenyl), g having the value 1 or 2 Is an integer, X is a polyvalent linking group that links one or two Q groups to the perfluoropolyether segment, X is divalent when g is 1 and trivalent when g is 2. And (C _a F _2a O) _f C _a F _2a is f units (C _a F _2a O) (wherein “a” of each unit is independently an integer of 1 to 4,
And f is a perfluoropolyether segment comprising a chain of a number) having a value of at least 2, and Z is -OC _a F _{2a + 1} or -XQ _g (wherein, a, X, Q and g are the An ethylenically unsaturated perfluoropolyether monomer having a) and 3. a hydrosilylation catalyst that results in the condensation of the polyorganohydrosiloxane and the ethylenically unsaturated perfluoropolyether monomer. An effective amount, and the molar ratio of the SiH group to the ethylenically unsaturated group is
A composition having a value of 0.5 to 1.3. 2. X is -CH ₂ OCH _2- , The composition according to claim (1) selected from: 3. The ethylenically unsaturated perfluoropolyether monomer, And _{H 2 C = CHCH 2 OCH 2} CF 2 O (CF 2 CF 2 O) m (CF 2 O) n CF 2 CH 2 OCH 2 CH = CH 2; in VIII (wherein, a, R ² and f are the And m and n are numbers each indicating the number of randomly distributed perfluoroethyleneoxy and perfluoromethyleneoxy repeating units, and m and n independently have the values 1 to 300. And the ratio m / n is 0.2 / 1 to 5/1). The composition according to claim (1) or (2).